NL8304321A - POLYARYLATES SHOWING IMPROVED RESISTANCE TO HEAT. - Google Patents

Description

S 2348-1272 Ned. ,. * P & c

Short designation: Polyarylates that have improved heat resistance I.

exhibit. I

Polyarylate resins are high molecular weight thermoplastic materials

weight which, due to their many advantageous properties, is increasing. I

find fit as architectural thermoplastic materials in many commerce

civil and industrial applications. Polyarylates are generally j

5 linear aromatic polymers containing recurring structural units of I.

aromatic ester in the polymer chain. In general, the I

polyarylates derived from divalent phenols and aromatic dicarboxylic acids I.

or their reactive derivatives. I

Although the conventional polyarylates are generally quite suitable I.

10 are for different applications, nevertheless there is a need, I.

especially in a high temperature environment, to polyarylates which, I.

to a large extent, the most advantageous properties of con- I

have conventional polyarylates, and at the same time have a higher resistance I.

against heat than the conventional polyarylates. I

It is therefore an object of the present invention to provide I.

polyarylates that are to a significant extent practically most of the beneficial I.

properties of conventional polyarylates while at the same time exhibiting improved heat resistance. I

According to the present invention, new polyaryl is provided

20, to a significant extent, leave practically most of the beneficial properties

shelves of conventional polyarylates, while simultaneously displaying I

exhibit improved heat resistance. The new polyarylates from I

the present invention are prepared from (i) at least one aromatic I

dicarboxylic acid; and (ii) at least one divalent phenol selected from certain I

25 specifically branched bivalent phenols. I

According to the present invention, new polyarylate resins are provided which exhibit improved heat resistance. These polyarylates I

are derived from (i) at least one aromatic dicarboxylic acid or a reactive derivative thereof, and (ii) at least one divalent phenol selected from certain specific branched divalent phenols.

The branched divalent phenols used in the preparation of the polyarylates of the present invention are selected from divalent phenols represented by the general formulas (1) and (2) of the formula sheet.

In formula (1), each R independently represents a halogen-35 atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxy group; 2

Each R independently represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; 8304321 * * - 2 - 3 R represents hydrogen or a monovalent hydrocarbon group; R5 and R5 independently represent monovalent hydrocarbon radicals, with the proviso that when R is hydrogen, at least one of the monovalent hydrocarbon radicals represented by R10 and R10 contains at least 5 carbon atoms; n and n 'independently represent one of the numbers 0,1, 2, 3 or 4.

1 2

In formula (2), R, R, n. and n 'as defined above.

7 R in formula (2) represents hydrogen or a monovalent hydrocarbon group 10, while R represents a divalent hydrocarbon group which, together with the carbon atom to which it is attached, forms a cyclic hydrocarbon structure.

1 2

The preferred halogen atoms represented by R and R are chlorine and bromine.

The monovalent hydrocarbon radicals represented by R and R are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups or 1 2 cycloalkyl groups. The preferred alkyl groups represented by R and R contain 1 to about 5 carbon atoms. These preferred alkyl groups include both straight and branched chain alkyl groups.

Some preferred non-limiting illustrative examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl groups, etc. Preferred aryl groups represented by R and R contain 6 to 12 carbon atoms, and include phenyl, naphthyl-1 2 or biphenyl groups. The preferred alkaryl and aralkyl groups represented by R and R contain from 7 to about 14 carbon atoms, and include

Preferred cycloalkyl groups represented by R and R contain 4 to about 8 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl groups and the like.

1 2

The hydrocarbonoxy groups represented by R and R are preferably selected from among others alkoxy and aryloxy groups. Preferred alkoxy groups contain 1 to about 6 carbon atoms. The preferred aryloxy group is the phenoxy group.

When more than 1 one R substituent is present in the divalent phenols of formulas (1) and (2), i.e. n: varies from 2 to 4, these 2 may be the same or different. The same goes for the R substituent. When n and n 'are 0, the ring carbon atoms of the aromatic group are substituted by hydrogen atoms.

3 4 5 7

The monovalent hydrocarbon radicals represented by R, R, R and R are selected from alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups.

3304321 * "» - - 3 - 3 4 5 7

The alkyl groups represented by R, R, R and R contain 1 to about 8 carbon atoms. These alkyl groups can be both branched and unbranched. Some nonlimiting illustrative examples of these preferred alkyl groups are methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, neopentyl groups, and the like.

3 4 5 7

The preferred aryl groups represented by R, R, R and R contain 6 to 12 carbon atoms, i.e. phenyl, naphthyl and biphenyl groups. The preferred alkaryl and aralkyl groups contain 7 to about 14 carbon atoms. Some nonlimiting illustrative examples of these preferred alkaryl and aralkyl groups include benzyl, tolyl, ethylphenyl groups and the like.

3 4 5 7

The preferred cycloalkyl groups represented by R, R, R and R contain from 4 to about 8 ring carbon atoms. Some nonlimiting illustrative examples of these preferred cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl groups, and the like.

g

As mentioned above, R is a divalent hydrocarbon group which, together with the group of formula (3), forms a cyclic hydrocarbon structure. This cyclic hydrocarbon structure can be mono- or bicyclic.

g

Preferably R is an alkylene group with 3 to about 7 carbon atoms, so that a ring structure is formed with 4 to about 8 ring carbon atoms. Some nonlimiting illustrative examples of alkylene groups represented by R include propylene, butylene, pentylene groups, and the like.

g

Some nonlimiting illustrative examples of the cyclic structures formed by R and the above-described group of the formula (3) to which the R is attached include groups of the formulas (4), (5), (6) and the like.

Particularly suitable - and sometimes even preferred - divalent 3 4 5 phenols of formula (1) are those in which each of R, R and R are independently selected from monovalent hydrocarbon groups.

The divalent phenols of formulas (1) and (2), as well as their method of preparation, are described in more detail in the Dutch patent application filed simultaneously with the present patent application by the same applicant (ref. Authorized: S 2348-1273 Ned.). Generally, the new bivalent phenols of formulas (1) and (2) are obtained by reacting a given aldehyde with a phenol in the presence of an acid as a catalyst. The particular aldehyde reagent is selected from aldehydes represented by the general formulas (7) and (8), wherein R ^, R ^, R ^, R ^ and R ^ have the same meaning as above. The phenolic reagents are selected from phenols produced by the general formulas (9}? - - 'T O -i

J v ·. C I

r * 4 * - 4 - 1 2 and (10) are represented, wherein R, R, n and n 'have the same meanings as above.

In order to obtain the divalent phenols of the formula (1), 1 mol of an aldehyde of the formula (7) is reacted with 1 mol of a phenol of the formula (9) and 1 mol of a phenol of the formula (10) in presence of an acid as a catalyst. Some non-limiting illustrative examples of suitable acidic catalysts that can be used include hydrochloric acid, hydrobromic acid, poly (styrene sulfonic acid), sulfuric acid, benzenesulfonic acid, etc. The phenols of formulas (9) and (10) and the aldehyde are left with formula (7) under such temperature pressure conditions. and "reacting" in the presence of the acidic catalyst to effect a common reaction between the phenols and the aldehyde to form the divalent phenol of formula (1). Generally, the reaction proceeds satisfactorily at about 1 atmosphere pressure and at temperatures from room temperature to about 100 ° C.

The amount of acid catalyst required is a catalytic amount. Catalytic amount is understood to mean an amount effective to catalyze the reaction between the aldehyde and the phenol.

Generally, this amount is in the range of about 0.1-10% by weight.

The phenols of formulas (9) and (10) can be the same. In that case, 1 mol of aldehyde of formula (7) is reacted with 2 mol of phenol.

In order to obtain the divalent phenol of formula (2), 1 mole of aldehyde of formula (8) is reacted with 1 mole of phenol of formula (9). And 1 mole of phenol of formula (10), or when the 2 phenols of formulas (9) and (10) are identical with 2: mole of phenol, under the reaction conditions and in the presence of an acidic catalyst as described above to make the divalent phenol of formula (2).

Some non-limiting illustrative examples of the divalent phenols represented by formula 30 (1) are the compounds of formulas (11) - (16), e; d.

Some nonlimiting illustrative examples of the divalent phenols represented by formula (2) are compounds of formulas (17) - (19) and the like.

In the preparation of the polyarylates of the present invention, only one of the divalent phenols of formulas (1) and (2) can be used. Alternatively, a mixture of 2 or more different of the divalent phenols of formula (1) and / or formula (2) may also be used. For example, one can use 2 or more different 8304321 * * - - 5 - divalent phenols of formula (1), 2 or more different divalent phenols of formula (2) can be used, or at least 1 divalent phenol of the formula (1) and at least 1 divalent phenol of the formula (2) can be used.

The aromatic dicarboxylic acids which are reacted with at least 1 divalent phenol selected from the divalent phenols represented by formulas (1) and (2) to prepare the polyarylates in question are known and are commercially available or readily available by from known methods. In general, any aromatic dicarboxylic acid normally used in the synthesis of polyesters can be used. These aromatic carboxylic acids are represented by the general formula (20), wherein Sr is a divalent aromatic group, preferably containing 6 to about 18 carbon atoms, such as phenylene, naphthylene, biphenylene, substituted phenylene, substituted naphthylene groups, and the like.

When these divalent aromatic groups are substituted, they are preferably substituted by alkyl groups or halogen atoms (preferably chlorine). In formula (20), Sr may also be a group of the type g -Ar'-R -Sr1. -, in which the symbols Ar 'are independently selected from the bivalent aromatic groups of the type described for Sr, 8, 20 and 2, an alkylene group with 2 to about 6 carbon atoms, an alkylidene group with 1 to about 6 carbon atoms, a cycloalkylidene group with 4 to about 7 ring carbon atoms or represents a cycloalkylene group with 4 to about 7 ring carbon atoms.

Preferred aromatic dicarboxylic acids are represented by the general formula (21) wherein R is independently selected from alkyl groups, preferably having 1 to about 6 carbon atoms, and halogen atoms, preferably chlorine or bromine, and p 0, 1, 2, 3 or 4.

9

When more than one R substituent is present in formula (21), they may be the same or different.

Some non-limiting illustrative examples of aromatic dicarboxylic acids represented by formula (21) include isophthalic acid, terephthalic acid, and the like.

In preparing the polyarylates in question, it is possible to use only one dicarboxylic acid of the formula (20), or to use a mixture of 2 or more different acids. For example, when the term aromatic dicarboxylic acid is used, it includes both individual aromatic dicarboxylic acids and mixtures of 2 or more aromatic dicarboxylic acids.

Instead of using the aromatic dicarboxylic acids themselves, it is also possible, and sometimes even preferable, to use their respective reactive derivatives. Preferred reactive derivatives are the acid dihalides, the acid dichlorides being preferred acid dihalides. For example, instead of using isophthalic acid, terephthalic acid or mixtures thereof, it is possible to use terephthaloyl chloride, isophthaloyl chloride or mixtures thereof.

The preparation of the polyarylates in question from the present divalent phenols and the aromatic dicarboxylic acids or their reactive derivatives can be carried out by known methods, such as, for example, heterogeneous interfacial polymerization, condensation polymerization in solution, condensation polymerization in the melt, etc.

Most conveniently, the polyarylates in question may be from equimolar or near equimolar amounts of (i) at least 1 divalent phenol selected from the divalent phenols represented by formulas (1) and (2) and (ii) at least 1 aromatic dicarboxylic acid or a reaction mixture can be prepared using the interfacial polymerization technique.

According to the conventional interfacial polymerization method, the reactants are present in various liquid phases that are immiscible and which form solvent environments when the polymer in question 2 is prepared. Thus, the divalent phenol is dissolved in 1 solvent, the aromatic dicarboxylic acid or its reactive derivative such as the acid dichloride is dissolved in the second solvent that is immiscible with the first, and the solutions are combined. Normally, an alkaline aqueous medium acts as a solvent for the divalent phenol, and an organic solvent is used as a solvent for the acid or acid dichloride, the organic solvent being chosen to either dissolve the prepared polyarylate or dissolve it as a swelling medium acts. Catalysts and chain stoppers or molecular weight regulators are also present during the reactions.

As catalysts in the interfacial polymerization process, any of the known catalysts which promote the interfacial polymerization reaction of the divalent phenol and the aromatic dicarboxylic acid or its reactive derivative may be used. Non-limiting examples of suitable catalysts are tertiary amines, quaternary ammonium compounds, quaternary phosphonium compounds and the like.

The usual molecular weight regulators may be of the known compounds which regulate the molecular weight of the polyarylate through a chain termination mechanism. Non-limiting examples of these compounds are phenol, t-butylphenol and the like.

8304321 t;

* - V

- - 7 -

The temperature at which the polymerization reaction takes place can vary from below 0 ° C to above 100 ° C. The polymerization reaction proceeds satisfactorily at temperatures from room temperature (25 ° C) to about 50 ° C.

The polyarylates of the present invention contain at least one recurring structural unit represented by the general formula (22) or (23).

When using only divalent phenols of the formula (1), the corresponding polyarylate contains only repeating structural units of the formula (22). When using only divalent phenols of formula (2), the corresponding polyarylate contains only repeating structural units of formula (23).

When divalent phenols of formulas (1) and (2) are used, the corresponding polyarylate contains recurring structural units of formulas (22) and (23).

The polyarylates of the present invention generally have a weight average molecular weight in the range of from about 10,000 to 200,000, preferably in the range of from about 20,000 to 100,000.

The polyarylates in question exhibit improved heat resistance, particularly improved second order transition temperatures up to the glass state (T) over the comparable conventional polyarylates known in the art, such as those derived from bisphenol-A ».

If desired, the polyarylates of the present invention may contain the well-known and conventional additives such as antioxidants, antistatic agents, fillers such as glass fibers, talc, mica, clay, etc., ultraviolet absorbers such as the benzophenones and the benzotriazones stabilizers against hydrolysis such as the epoxides described in U.S. Pat. Nos. 3,489,716, 4,138,379 and 3,839,247, color stabilizers such as organophosphites, flame retardants, etc.

Some particularly useful flame retardants are the alkali and alkaline earth metal salts of sulfonic acids. These types of flame retardants are described in U.S. Pat. No. 3,933,734, 3,948,851, 3,926,908, 3,919,167, 3,909,490, 3,953,396, 3,931,100, 3 3,978,024, 3,953 .399, 3,917,559, 3,951,910 and 3,940,366.

Another embodiment of the present invention is a polyarylate prepared from (i) at least one aromatic dicarboxylic acid or a reactive derivative thereof, (ii) at least one divalent phenol of the general formula (1) or (2) and (iii ) at least one conventional bivalent phenol, 8304321-8 - represented by the general formula (24), wherein: A is a straight chain alkylene chain ,. preferably with 2 to about 6 carbon atoms, a straight-chain alkylidene group, preferably with 1 to about 6 carbon atoms, a cycloalkylene group, preferably with 4 to about 7 ring-5 carbon atoms, a cycloalkylidene group, preferably with 4 to 7 ring carbon atoms, -S-, -SS-, -O-, -CO-, -SO- or ~ so2 ~; each X independently represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; each X 'independently represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; a and a 'independently represent one of the numbers 0, 1, 2, 3 or 4'; and b is 0 or 1.

The monovalent hydrocarbon groups represented by X and X 'include straight chain or branched alkyl groups, preferably with 1 to about 6 carbon atoms, aryl groups, preferably with 6 to 12 carbon atoms such as phenyl, naphthyl and diphenyl groups, alkaryl and aralkyl groups, preferably with 7 to about 14 carbon atoms, and cycloalkyl groups, preferably with 4 to about 7 ring carbon atoms.

The preferred halogen atoms represented by X and X 'are chlorine and bromine.

The preferred monovalent hydrocarbonoxy groups represented by X and X 'are the alkoxy groups, preferably having 1 to about 6 carbon atoms, and the aryloxy groups, preferably a phenoxy group.

When there is more than one X substituent in the divalent phenols represented by formula (24), they may be the same or different. The same goes for the X 'substituent. When there is an X and an X 'substituent ">. \", These can be the same or different.

When in formula (24) b is 0, the aromatic rings are directly connected without any intermediate alkylene group or other bridge portion.

Some nonlimiting illustrative examples of suitable divalent phenols of the formula (24) include

2,2-bis (4-hydroxyphenyl) propane (bisphenol-A), 1,1-bis (4-hydroxyphenyl) cyclohexane, 35 bis (3-methyl-4-hydroxyphenyl) methane, 4,4'-thiodiphenol, bis (3.5 -dimethyl-4-hydroxyphenyl) sulfone, 2,2-bis (3,3-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-5-methyl-4-hydroxyphenyl) propane, etc.

8304321 »♦ <· - 9 -

In this embodiment of the invention, the divalent phenol or phenol mixture of formula (1) and / or (2) is used in an amount effective to improve the heat resistance of the polyarylate. Generally, this amount is in the range of about 10-90 wt%, preferably about 20-80 wt%, based on the total amount of divalent phenols used.

The method of preparation of the polyarylates in this embodiment is generally similar to that described above, except that the divalent phenol of formula (24) is present in the reaction mixture.

The polyarylates in this embodiment exhibit improved heat resistance compared to conventional polyarylates, while at the same time retaining substantially most of the beneficial properties of the conventional polyarylates.

If desired, the various additives described above can be mixed with the polyarylates of this embodiment.

Yet another embodiment of the present invention is a physical mixture of (i) at least one polyarylate of the present invention, ie derived from (a) at least one of the divalent phenols represented by formulas 20 (1) and (2) , and (b) at least one aromatic carboxylic acid (hereinafter referred to as polyarylate resin A), and (ii) at least one conventional polyarylate, ie, derived from (a) at least one aromatic dicarboxylic acid, and (b) at least one of the by formula (24) proposed bivalent phenols (hereinafter referred to as polyarylate resin B).

These blends contain an amount of resin A which is effective to improve the heat resistance of the blends. Generally, this amount is in the range of about 10-90% by weight, based on the total amount of resins A and B present in the mixture.

The blends in this embodiment exhibit improved heat resistance over blends in conventional polyarylates.

The method of mixing resins A and B is not critical, and is not part of the invention. For example, one method of preparing the blends in question involves mixing the two resins in powder or granular form, extruding the mixture, chopping and re-extruding.

If desired, the additives described above can be mixed with the mixtures of the invention.

The following non-limiting examples illustrate the invention. Unless otherwise stated, the stated parts or percentages are respectively ...................

8304321 ψ - 10 - parts by weight or percentages by weight.

EXAMPLE I

This example illustrates the preparation of 4,4 '- (cyclohexylmethylene) bisphenol, a divalent phenol of the formula (2).

5 In a warm solution of 658.7 g (7 mol) of molten phenol and 78.9 g (0.7 mol) of cyclohexane carboxaldehyde (hexahydrobenzaldehyde), which is contained in a 2 l three-necked flask equipped with a stirrer, thermometer, reflux condenser and gas inlet tube extending below the liquid surface, chlorinated hydrogen gas was passed while ensuring that the temperature of the reaction mixture, which obtained a reddish orange color, was maintained between 34 ° C and 45 ° C using a cold water cooling bath . After saturating the solution with hydrogen chloride, it was left overnight at ambient temperature, during which time a white solid formed which was filtered off, triturated with dichloromethane and filtered again. The resulting white crystals, with a melting point between 216 ° C and 218 ° C, were recrystallized from methanol-water, after which they had a melting point of 221-222 ° C.

EXAMPLE II

This example illustrates the preparation of a polyarylate of the present invention.

To a slurry of 4.2 g (0.015 mol) 4.4 '- (cyclohexylmethylene) bisphenol, which was prepared practically according to the procedure of Example I, 0.03 g (2 mol%) of triethylamine, 0.015 g (1 mol%) Phenol, 400 ml of dichloromethane and 300 ml of water were added with sufficient 25% sodium hydroxide solution to raise the pH to 11. A solution of 3.04 g (0.015 mol) of isophthaloyl dichloride in 20 ml of dichloromethane was then added over 10 minutes, followed by stirring for 10 minutes.

The dichloromethane phase was separated, washed with 0.01 N hydrochloric acid, followed by washing with deionized water. The organic layer 30 was then separated and dried with silica gel. Addition of an excess of methanol precipitated the polymer, which had a second order glass transition temperature of 216.8 ° C.

In contrast to the T of 216.8 ° C of the polyarylate in Example 2, a conventionally known polyarylate prepared from bisphenol-A and isophthalic acid (isophthaloyl dichloride) exhibits one of about 180 ° C.

Thus, the present polyarylates exhibit improved heat resistance over conventionally known polyarylates, as evidenced by the improved T values.

g

Of course, numerous modifications 40 are possible within the scope of the invention.

_______.

8304321

Claims (26)

A polyarylate material exhibiting improved heat resistance, characterized in that it contains at least one polyarylate resin derived from 5 (a) at least one aromatic dicarboxylic acid or a reactive derivative thereof, and (b) at least one divalent phenol of the general formulas ( 1) or (2), wherein: each R independently represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxy group, 2 Each R independently represents a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbon oxy group, 3 R a hydrogen atom or a monovalent hydrocarbon group, 4 5 R and R independently represent monovalent hydrocarbon groups 3 15, with the proviso that when R is a hydrogen atom, at least one of the monovalent hydrocarbon groups represented by R and R has at least 2 carbon atoms contains, 6 R a divalent hydrocarbon radical lt which forms a ring structure together with the carbon atom to which R 2 is bonded, 7 2. Material according to claim 1, characterized in that the hydrocarbon groups represented by R * and 25 represent alkyl, aryl, aralkyl, alkaryl, or cycloalkyl groups. Material according to claim 1, characterized in that the halogen atoms represented by R * 2 and R are chlorine or bromine atoms. Material according to claim 1, characterized in that the hydrocarbon groups represented by R 2 and R 2 represent alkoxy or aryloxy groups. 3 5. Material according to claims 1-4, characterized in that the hydrocarbon groups represented by R, 4, 7, R, R and R are alkyl, aryl, alkaryl, aralkyl or cycloalkyl groups. 6. Material according to claims 1-5, characterized in that the hydrocarbon group represented by R35 is an alkylene group. 3 4 5 Material according to claims 1-6, characterized in that R, R and R are independently monovalent hydrocarbon groups. Material according to claims 1-5 and 7, characterized in that the divalent phenol is represented by the general formula (1}. 8 'K o /. Τ λ 1 ö v; 0 £. I V - 12 - · The material according to claims 1-6, characterized in that the divalent phenol is represented by the general formula (2). g The material according to claim 9, characterized in that the divalent hydrocarbon group represented by R is pentylene. 7 Material according to claim 9 or 10, characterized in that R represents hydrogen. Material according to claims 1-11, characterized in that the reactive derivative of the aromatic dicarboxylic acid is isophthaloyl dichloride. 13. Material according to claims 1-12, characterized in that n and n 'are both 10. Material according to claims 1 to 13, characterized in that the polyaryl resin is derived from the components (a) and (b) of claim 1, and furthermore a bivalent represented by the general formula (24): -pheno 1 in which : 15. a straight-chain alkyl one group with 2 to about 6 carbon atoms, a straight-chain alkylidene group with 1 to about 6 carbon atoms, a cycloalkylene group with 4 to about 7 ring carbon atoms, a cycloalkylidene group with 4 to 7 ring carbon atoms, -S- , -SS-, -O-, -CO-, -SO- or -SO2 ~; each X represents independently a halogen atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; Veen represents each X 'independently of each halos atom, a monovalent hydrocarbon group or a monovalent hydrocarbonoxy group; b 0 or. 1; and a and a 'independently represent one of the numbers 0, 1, 2, 3 or 4. Material according to claim 14, characterized in that the amount of divalent phenol (b) is an effective amount to improve the heat resistance of the material. Material according to claim 15, characterized in that the amount (b) of about 10-90 wt. %, based on the total amount of divalent phenols used. Material according to claims 14-16, characterized in that b = 1. 18. Material according to claims 14-17, characterized in that A represents an alkylene, an alkylidene, a cycloalkylene or a cycloalkylidene group. The material according to claims 1 to 13, characterized in that it further contains at least one polyarylate resin derived from (a) at least one aromatic dicarboxylic acid or a reactive derivative thereof and 8304321 - ^ - rx - 13 - (b) at least one divalent phenol of the general formula (24) wherein the different symbols have the meanings given in claim 14. Material according to claim 19, characterized in that the resin according to claims 1-13 is present in an amount effective to improve the heat resistance of the material. 20 R. represents a hydrogen atom or a monovalent hydrocarbon group, and n and n 'independently represent one of the numbers 0, 1, 2, 3 or 4. Material according to claim 20, characterized in that the amount of this resin is about 10-90% by weight, based on the total amount of the two resins present. Material according to claims 19-21, characterized in that b = 1. A material according to claims 19-22, wherein A represents an alkylene, an alkylidene, a cycloalkylene or a cycloalkylidene group. Material according to claims 19-23, characterized in that the divalent phenol of formula (24) is bisphenol-A. The material according to claim 8, characterized in that the divalent phenol is a 4,4'-bisphenol. The material according to claim 9, characterized in that the divalent is a 4,4'-bisphenol. 8304321